CN111879833A - 一种异丙甲草胺分子印迹电化学传感器的制备方法 - Google Patents

一种异丙甲草胺分子印迹电化学传感器的制备方法 Download PDF

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CN111879833A
CN111879833A CN202010767053.1A CN202010767053A CN111879833A CN 111879833 A CN111879833 A CN 111879833A CN 202010767053 A CN202010767053 A CN 202010767053A CN 111879833 A CN111879833 A CN 111879833A
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molecularly imprinted
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刘本志
肖波
潘梅
王敏
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Yancheng Institute of Technology
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    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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Abstract

一种异丙甲草胺分子印迹电化学传感器的制备方法，是以处理过的FTO玻璃电极作为基底，采用石墨烯修饰FTO玻璃电极，在亚甲基绿和吡咯双功能单体和异丙甲草胺的磷酸盐缓冲溶液中电聚合形成分子印迹聚合物制得，并用异丙醇/乙酸溶液去除模板，得到对异丙甲草胺选择性响应的分子印迹电化学传感器。这种方法制备出的分子印迹电化学传感器对异丙甲草胺的检出限为1.1×10‑7 mol/L，线性范围为1.5×10‑6 mol/L‑8.0×10‑5 mol/L。本发明中提供的方法制备出的分子印迹电化学传感器具有良好的稳定性和选择性，而且制备方法简单实用。

Description

一种异丙甲草胺分子印迹电化学传感器的制备方法
技术领域
本发明涉及的是电化学传感器领域，具体涉及的是异丙甲草胺分子印迹电化学传感器的制备方法。
背景技术
异丙甲草胺是广谱性播后苗前除草剂，主要通过幼芽吸收，向上传导，抑制幼芽与根的生长。作用机制主要是抑制发芽种子的蛋白质合成，其次抑制胆碱渗入磷脂，干扰卵磷脂形成。作为除草剂，若过度使用，大量残留在农作物和土壤、水体环境中，会对人体健康以及生态环境造成危害。
异丙甲草胺的现行检测方法主要有气相色谱法、液相色谱法、气相色谱-串联质谱法和高效液相色谱-串联质谱法等。这类检测方法所需设备昂贵，并需要经过培训的专业人员进行操作，难以达到快速检测的要求。研究快速、便捷、低成本的异丙甲草胺检测方法具有重要的意义。
分子印迹技术是一种制备对模板分子具有识别性能的聚合物的技术。分子印迹聚合物（MIPs）对模板分子的识别具有特异识别性、构效预定性和广泛实用性等特点。分子印迹聚合物具有化学稳定性好、选择性高和容易制备等特点。分子印迹电化学传感器就是将电化学传感器检测快速、操作简单的优势与分子印迹技术相结合，可用于对异丙甲草胺的选择性检测。
发明内容
发明目的：本发明的目的是提供一种异丙甲草胺分子印迹电化学传感器简易的制备方法，这种方法可用于解决分子印迹电化学传感器的制备过程复杂，稳定性差等问题。
技术方案：本发明采用如下的技术方案。
这种异丙甲草胺分子印迹电化学传感器的制备方法是以处理过的FTO玻璃电极作为基底，采用石墨烯修饰FTO玻璃电极，亚甲基绿和吡咯双功能单体和异丙甲草胺的磷酸盐缓冲溶液溶液作为电解质，利用循环伏安法聚合形成分子印迹聚合物制得，这种方法制备出的分子印迹电化学传感器对异丙甲草胺的检出限为1.1×10-7 mol/L，线性范围为1.5×10-6 mol/L-8.0×10-5 mol/L，具体制备方法包括以下步骤：
步骤一：将FTO玻璃电极依次用丙酮，乙醇和去离子水中分别超声洗涤数分钟。然后将电极在K3Fe(CN)6中扫描，得到可逆的循环伏安峰，证明电极处理好。
步骤二：将石墨烯分散到混酸溶液（HNO3 : H2SO4=1:3）中回流完成对石墨烯表面的羧基化修饰；然后，过滤、洗涤、烘干；将获得的产物超声分散得到悬浮液；取5μL-25μL悬浮液滴涂到处理好的FTO玻璃电极表面，形成均匀分散层，自然晾干，得到石墨烯修饰电极。
步骤三：将亚甲基绿和吡咯双功能单体和异丙甲草胺溶解在磷酸盐缓冲溶液溶液中，混合均匀，亚甲基绿和吡咯双功能单体和异丙甲草胺的摩尔比为(1-6):(1-6):1。
步骤四：将步骤三中混合好的溶液作为电解质溶液，然后将石墨烯修饰的电极置于混合溶液中，进行电化学聚合形成分子印迹聚合物，用异丙醇/乙酸溶液洗脱异丙甲草胺后，得到异丙甲草胺的分子印迹电化学传感器。
上述方案中，磷酸盐缓冲溶液溶液的pH为2-7。
上述方案中电化学聚合方法为电沉积法，沉积电位为0.2V-1.2V，沉积时间为90s-720s。
上述方案中异丙醇/乙酸溶液浓度为1:1-12:1。
上述方法制备的异丙甲草胺分子印迹电化学传感器可用于水体中异丙甲草胺的定量检测。
具体实施方式
实施例1
FTO玻璃电极预处理
将FTO玻璃电极依次用丙酮，乙醇和去离子水中分别超声洗涤数分钟。然后将电极于K3Fe(CN)6中扫描，得到可逆的循环伏安峰，证明电极处理好。
实施例2
石墨烯修饰FTO玻璃电极
将石墨烯分散到混酸溶液（HNO3 : H2SO4=1:3）中回流完成对石墨烯表面的羧基化修饰；然后，过滤、洗涤、烘干；将获得的产物超声分散得到悬浮液；取5μL-25μL悬浮液滴涂到处理好的FTO玻璃电极表面，形成均匀分散层，自然晾干，得到石墨烯修饰电极。
实施例3
配制聚合溶液
以异丙甲草胺作为模板分子，亚甲基绿和吡咯双功能单体作为功能单体，充分溶解在磷酸盐缓冲溶液溶液中，亚甲基绿和吡咯双功能单体和异丙甲草胺的摩尔比为(1-6):(1-6):1。
实施例4
电化学聚合
将石墨烯修饰的FTO玻璃电极置于所制得的聚合溶液中进行电聚合，工作电极为石墨烯修饰的FTO玻璃电极，参比电极为Ag/AgCl电极，辅助电极为铂丝电极；电化学聚合方法为电沉积法，沉积电位为0.2V-1.2V，沉积时间为90s-720s。
实施例5
将所制得的聚合物电极置于异丙醇/乙酸溶液中洗脱60min，然后将洗脱后的电极用蒸馏水冲洗，在室温下晾干备用。
实施例6
工作曲线的绘制
采用方波伏安法进行异丙甲草胺的浓度测定实验。方波伏安法起止电位为-0.3 V-0.6V，电位增量0.005 V，方波频率15Hz，方波幅度0.1V，检测底液为3.0 mM K3[Fe(CN)6]和0.1M KCl。每次使用后，将电极浸在异丙醇/乙酸溶液中，用磁力搅拌器洗脱30min，去除聚合膜中吸附的模板分子，以便重复使用。根据己知异丙甲草胺的浓度与方波伏安峰电流的差值绘制标准曲线，检出限为1.1×10-7 mol/L，线性范围为1.5×10-6 mol/L-8.0×10-5 mol/L。

Claims (5)

1.一种异丙甲草胺分子印迹电化学传感器的制备方法，其特征在于这种异丙甲草胺分子印迹电化学传感器的制备方法是以石墨烯修饰的FTO玻璃电极作为基底，在亚甲基绿和吡咯双功能单体和异丙甲草胺的磷酸盐缓冲溶液中电聚合形成分子印迹聚合物制得，这种方法制备出的分子印迹电化学传感器对异丙甲草胺的检出限为1.1×10-7 mol/L，线性范围为1.5×10-6 mol/L-8.0×10-5 mol/L；制备方法包括以下步骤：（一）将FTO玻璃电极依次用丙酮，乙醇和去离子水中分别超声洗涤数分钟，然后将电极于K3Fe(CN)6中扫描，得到可逆的循环伏安峰，证明电极处理好；然后将分散好的石墨烯悬浮液滴加到FTO玻璃电极上，形成均匀分散层，自然晾干，得到石墨烯修饰的电极；（二）将亚甲基绿和吡咯双功能单体和异丙甲草胺溶解在磷酸盐缓冲溶液中，混合均匀，亚甲基绿和吡咯双功能单体和异丙甲草胺的摩尔比为(1-6):(1-6):1；（三）将前面混合好的溶液作为电解质溶液，把石墨烯修饰的电极置于混合溶液中，进行电化学聚合形成分子印迹聚合物，用异丙醇/乙酸溶液洗去异丙甲草胺模板分子，得到异丙甲草胺的分子印迹电化学传感器。
2.根据权利要求1所述的异丙甲草胺分子印迹电化学传感器的制备方法，其特征在于，所述的制备方法中电解质溶液为磷酸盐缓冲溶液溶液，pH为2-7。
3.根据权利要求1所述的异丙甲草胺分子印迹电化学传感器的制备方法，其特征在于，所述的制备方法中滴加到FTO玻璃电极上的石墨烯悬浮液的量为5μL-25μL。
4.根据权利要求1所述的异丙甲草胺分子印迹电化学传感器的制备方法，其特征在于，所述的制备方法中电化学聚合方法为电沉积法，沉积电位为0.2V-1.2V，沉积时间为90s-720s。
5.根据权利要求1所述的异丙甲草胺分子印迹电化学传感器的制备方法，其特征在于，所述的制备方法中异丙醇/乙酸溶液浓度为1:1-12:1。
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